Crystal-Interface-Mediated Self-Assembly of ZnIn₂S₄/CdS S-scheme Heterojunctions Toward Efficient Photocatalytic Hydrogen Production

Abstract

Efficient photocatalytic water splitting can be significantly enhanced through the careful design of S-scheme heterostructures, which play a pivotal role in optimizing performance. Herein, we report the construction of ZnIn₂S₄/CdS S-scheme heterojunctions under ambient conditions, based on a sonochemical strategy. This structure is facilitated by the well-matched interface between the (007) plane of layered ZnIn₂S₄ and the (101) plane of CdS, leading to a threshold optical response of 2.12 eV, which optimally aligns with visible light absorption. As a proof of concept, the resulting ZnIn₂S₄/CdS catalysts demonstrate a remarkable improvement in photocatalytic H₂ evolution, achieving a rate of 5678.2 μmol h⁻¹g⁻¹ under visible light irradiation (λ > 400 nm). This rate is approximately 10 times higher than that of pristine ZnIn₂S₄ nanosheets (NSs) and about 4.6 times higher than that of CdS nanoparticles (NPs), surpassing the performance of most ZnIn₂S₄-based photocatalysts reported to date. Moreover, they deliver a robust photocatalytic performance during long-term operation of up to 60 h, showing their potential for use in practical applications. Based on the theoretical calculation and experimental results, it is verified that the movements of electrons and holes in the opposite direction could be induced by the disparity in the work function and the internal electric field within the interfaces, thus facilitating the construction of S-scheme heterojunctions, which fundamentally suppresses carrier recombination while minimizing photocorrosion of ZnIn₂S₄ toward enhanced photocatalytic behaviors.

Keywords

CdS / heterojunctions / interface / photocatalytic hydrogen production / ZnIn2S4

References

[1] T. Hisatomi and K. Domen, “Reaction Systems for Solar Hydrogen Production via Water Splitting With Particulate Semiconductor Photocatalysts,” Nature Catalysis 2, no. 5 (2019): 387-399.

[2] D. Zhang, J. Teng, H. Yang, et al., “Air-Condition Process for Scalable Fabrication of CdS/ZnS 1D/2D Heterojunctions Toward Efficient and Stable Photocatalytic Hydrogen Production,” Carbon Energy 5, no. 7 (2022): e277.

[3] Q. Wang and K. Domen, “Particulate Photocatalysts for Light-Driven Water Splitting: Mechanisms, Challenges, and Design Strategies,” Chemical Reviews 120, no. 2 (2019): 919-985.

[4] X. Wang, X. Wang, J. Huang, S. Li, A. Meng, and Z. Li, “Interfacial Chemical Bond and Internal Electric Field Modulated Z-Scheme S_v-ZnIn₂S₄/MoSe₂ Photocatalyst for Efficient Hydrogen Evolution,” Nature Communications 12, no. 1 (2021): 4112.

[5] X. Chen, S. Shen, L. Guo, and S. S. Mao, “Semiconductor-Based Photocatalytic Hydrogen Generation,” Chemical Reviews 110, no. 11 (2010): 6503-6570.

[6] Z. Wang, C. Li, and K. Domen, “Recent Developments in Heterogeneous Photocatalysts for Solar-Driven Overall Water Splitting,” Chemical Society Reviews 48, no. 7 (2019): 2109-2125.

[7] J. Qiu, K. Meng, Y. Zhang, et al., “COF/In₂S₃ S-Scheme Photocatalyst With Enhanced Light Absorption and H₂O₂-Production Activity and fs-Ta Investigation,” Advanced Materials 36, no. 24 (2024): e2400288.

[8] L. Zhang, J. Zhang, H. Yu, and J. Yu, “Emerging S-Scheme Photocatalyst,” Advanced Materials 34, no. 11 (2022): e2107668.

[9] Q. Xu, L. Zhang, B. Cheng, J. Fan, and J. Yu, “S-Scheme Heterojunction Photocatalyst,” Chem 6, no. 7 (2020): 1543-1559.

[10] B. Zhu, J. Sun, Y. Zhao, L. Zhang, and J. Yu, “Construction of 2D S-Scheme Heterojunction Photocatalyst,” Advanced Materials 36, no. 8 (2024): e2310600.

[11] L. Wang, B. Zhu, J. Zhang, J. B. Ghasemi, M. Mousavi, and J. Yu, “S-Scheme Heterojunction Photocatalysts for CO₂ Reduction,” Matter 5, no. 12 (2022): 4187-4211.

[12] C. Cheng, B. He, J. Fan, B. Cheng, S. Cao, and J. Yu, “An Inorganic/Organic S-Scheme Heterojunction H₂-Production Photocatalyst and Its Charge Transfer Mechanism,” Advanced Materials 33, no. 22 (2021): e2100317.

[13] C. Nie, X. Wang, P. Lu, Y. Zhu, X. Li, and H. Tang, “Advancements in S-Scheme Heterojunction Materials for Photocatalytic Environmental Remediation,” Journal of Materials Science & Technology 169 (2024): 182-198.

[14] P. Zhou, J. Yu, and M. Jaroniec, “All-Solid-State Z-Scheme Photocatalytic Systems,” Advanced Materials 26, no. 29 (2014): 4920-4935.

[15] T. Li, N. Tsubaki, and Z. Jin, “S-Scheme Heterojunction in Photocatalytic Hydrogen Production,” Journal of Materials Science & Technology 169 (2024): 82-104.

[16] L. Wang, B. Cheng, L. Zhang, and J. Yu, “In Situ Irradiated XPS Investigation on S-Scheme TiO₂@ZnIn₂S₄ Photocatalyst for Efficient Photocatalytic CO₂ Reduction,” Small 17, no. 41 (2021): e2103447.

[17] S. Wang, Y. Wang, S. L. Zhang, S. Q. Zang, and X. W. Lou, “Supporting Ultrathin ZnIn₂S₄ Nanosheets on Co/N-Doped Graphitic Carbon Nanocages for Efficient Photocatalytic H₂ Generation,” Advanced Materials 31, no. 41 (2019): 1903404.

[18] C. Hao, Y. Tang, W. Shi, F. Chen, and F. Guo, “Facile Solvothermal Synthesis of a Z-Scheme 0D/3D CeO₂/ZnIn₂S₄ Heterojunction With Enhanced Photocatalytic Performance Under Visible Light Irradiation,” Chemical Engineering Journal 409 (2021): 128168.

[19] Z. Wang, B. Su, J. Xu, Y. Hou, and Z. Ding, “Direct Z-Scheme ZnIn₂S₄/LaNiO₃ Nanohybrid With Enhanced Photocatalytic Performance for H₂ Evolution,” International Journal of Hydrogen Energy 45, no. 7 (2020): 4113-4121.

[20] S. Wang, B. Y. Guan, X. Wang, and X. W. D. Lou, “Formation of Hierarchical Co₉S₈@ZnIn₂S₄ Heterostructured Cages as an Efficient Photocatalyst for Hydrogen Evolution,” Journal of the American Chemical Society 140, no. 45 (2018): 15145-15148.

[21] H. Liu, J. Zhang, and D. Ao, “Construction of Heterostructured ZnIn₂S₄@NH₂-MIL-125(Ti) Nanocomposites for Visible-Light-Driven H₂ Production,” Applied Catalysis, B: Environmental 221 (2018): 433-442.

[22] H. Peng, H. Yang, J. Han, et al., “Defective ZnIn₂S₄ Nanosheets for Visible-Light and Sacrificial-Agent-Free H₂O₂ Photosynthesis via O₂/H₂O Redox,” Journal of the American Chemical Society 145, no. 50 (2023): 27757-27766.

[23] C. Chen, W. Hou, and Y. Xu, “Significantly Increased Production of H₂ on ZnIn₂S₄ Under Visible Light Through Co-Deposited CoWO₄ and Co₃O₄,” Applied Catalysis, B: Environmental 316 (2022): 121676.

[24] W. Yang, L. Zhang, J. Xie, et al., “Enhanced Photoexcited Carrier Separation in Oxygen-Doped ZnIn₂S₄ Nanosheets for Hydrogen Evolution,” Angewandte Chemie International Edition 55, no. 23 (2016): 6716-6720.

[25] Y. Zhang, Y. Wu, L. Wan, et al., “Hollow Core-Shell Co₉S₈@ZnIn₂S₄/CdS Nanoreactor for Efficient Photothermal Effect and CO₂ Photoreduction,” Applied Catalysis, B: Environmental 311 (2022): 121255.

[26] Z. Gao, K. Chen, L. Wang, B. Bai, H. Liu, and Q. Wang, “Aminated Flower-Like ZnIn₂S₄ Coupled With Benzoic Acid Modified G-C₃N₄ Nanosheets via Covalent Bonds for Ameliorated Photocatalytic Hydrogen Generation,” Applied Catalysis, B: Environmental 268 (2020): 118462.

[27] J. He, G. Zhang, Y. Jiang, J. Jia, and J. Cao, “Design and Synthesis of Two Dimensional-ZnIn₂S₄ Nanosheets With Sulfur Vacancies for Improving Photocatalytic Hydrogen Production Performance,” Progress in Natural Science: Materials International 33, no. 5 (2023): 607-615.

[28] C. Q. Li, X. Du, S. Jiang, et al., “Constructing Direct Z-Scheme Heterostructure by Enwrapping ZnIn₂S₄ on CdS Hollow Cube for Efficient Photocatalytic H₂ Generation,” Advanced Science 9, no. 24 (2022): 2201773.

[29] Z. Li, X. Wang, W. Tian, A. Meng, and L. Yang, “CoNi Bimetal Cocatalyst Modifying a Hierarchical ZnIn₂S₄ Nanosheet-Based Microsphere Noble-Metal-Free Photocatalyst for Efficient Visible-Light-Driven Photocatalytic Hydrogen Production,” ACS Sustainable Chemistry & Engineering 7, no. 24 (2019): 20190-20201.

[30] G. Sun, Z. Tai, F. Li, et al., “Construction of ZnIn₂S₄/CdS/PdS S-Scheme Heterostructure for Efficient Photocatalytic H₂ Production,” Small 19, no. 27 (2023): 2207758.

[31] X. Wu, G. Chen, L. Li, J. Wang, and G. Wang, “ZnIn₂S₄-Based S-Scheme Heterojunction Photocatalyst,” Journal of Materials Science & Technology 167 (2023): 184-204.

[32] P. Lu, K. Liu, Y. Liu, et al., “Heterostructure With Tightly-Bound Interface Between In₂O₃ Hollow Fiber and ZnIn₂S₄ Nanosheet Toward Efficient Visible Light Driven Hydrogen Evolution,” Applied Catalysis, B: Environmental 345 (2024): 123697.

[33] X. Tao, Y. Gao, S. Wang, et al., “Interfacial Charge Modulation: An Efficient Strategy for Boosting Spatial Charge Separation on Semiconductor Photocatalysts,” Advanced Energy Materials 9, no. 13 (2019): 1803951.

[34] Y. Guo, W. Shi, and Y. Zhu, “Internal Electric Field Engineering for Steering Photogenerated Charge Separation and Enhancing Photoactivity,” EcoMat 1, no. 1 (2019): e12007.

[35] J. P. Perdew, K. Burke, and M. Ernzerhof, “Generalized Gradient Approximation Made Simple,” Physical Review Letters 77, no. 18 (1996): 3865-3868.

[36] G. Kresse and J. Furthmüller, “Efficient Iterative Schemes for Ab Initio Total-Energy Calculations Using a Plane-Wave Basis Set,” Physical Review B 54, no. 16 (1996): 11169-11186.

[37] G. Kresse and D. Joubert, “From Ultrasoft Pseudopotentials to the Projector Augmented-Wave Method,” Physical Review B 59, no. 3 (1999): 1758-1775.

[38] C.-Q. Li, S.-S. Yi, Y. Liu, Z. L. Niu, X. Z. Yue, and Z. Y. Liu, “In-Situ Constructing S-Scheme/Schottky Junction and Oxygen Vacancy on SrTiO₃ to Steer Charge Transfer for Boosted Photocatalytic H₂ Evolution,” Chemical Engineering Journal 417 (2021): 129231.

[39] X. Yue, S. Yi, R. Wang, Z. Zhang, and S. Qiu, “A Novel Architecture of Dandelion-Like Mo₂C/TiO₂ Heterojunction Photocatalysts Towards High-Performance Photocatalytic Hydrogen Production From Water Splitting,” Journal of Materials Chemistry A 5, no. 21 (2017): 10591-10598.

[40] H. Jing, L. Chen, S. Yi, T. Li, J. Sun, and D. Chen, “Comparative Insight Into Effect of Hybridizing Potassium and Hydrogen Ions on Photocatalytic Reduction/Oxidization Behavior of g-C₃N₄ Nanocrystals,” Chemical Engineering Journal 417 (2021): 129187.

[41] C. Chen, W. Ma, and J. Zhao, “Semiconductor-Mediated Photodegradation of Pollutants Under Visible-Light Irradiation,” Chemical Society Reviews 39, no. 11 (2010): 4206.

[42] J. Hu, D. Chen, Z. Mo, et al., “Z-Scheme 2D/2D Heterojunction of Black Phosphorus/Monolayer Bi₂WO₆ Nanosheets With Enhanced Photocatalytic Activities,” Angewandte Chemie International Edition 58, no. 7 (2019): 2073-2077.

[43] G. Zhang, D. Chen, N. Li, et al., “Preparation of ZnIn₂S₄ Nanosheet-Coated CdS Nanorod Heterostructures for Efficient Photocatalytic Reduction of Cr(VI),” Applied Catalysis, B: Environmental 232 (2018): 164-174.

RIGHTS & PERMISSIONS

2025 The Author(s). Carbon Energy published by Wenzhou University and John Wiley & Sons Australia, Ltd.